APPLICATION NOTE

Temperature-Dependent Phase Transitions of ZrO2

The temperature-induced phase transition from monoclinic to tetragonal ZrO2 is predicted from
first principles calculations using a quasi-harmonic approach for the vibrational enthalpy and
entropy. The computed transition temperature is within 15% of the experimental value. Relative
trends due to vacancies, alloying elements, and mechanical stress can be expected to have a higher
accuracy. The present results show the importance of thermal expansion, which is here also
obtained from first principles.

Keywords: zirconia, phase transition, computations, first-principles, phonon, vibrations,

entropy, thermal expansion

Experimental Facts tetragonal structure becomes thermodynamically

stable. At 2650 K the tetragonal structure
At low temperatures, the most stable phase of
changes into a cubic calcium fluoride structure.
ZrO2 is a monoclinic form, which occurs
The mineral name zirconia is used for both the
naturally as the mineral Baddeleyite. At a
tetragonal and the cubic structures. ZrO2 melts
temperature of 1478 K and ambient pressure, a
at 2983 K (cf. Fig. 1).

cubic 2650 K

1478 K
tetragonal

monoclinic

Figure 1. O-Zr phase diagram (after Ref. 1) and structures of ZrO2 in the room temperature (rt)
monoclinic phase, the high temperature (ht1) tetragonal phase and the high temperature (ht2) cubic
phase. The phase transitions are observed at 1205 C (1478 K) and 2377 C (2650 K).

Copyright Materials Design 2009

Materials Design Application Note Phase Transitions in ZrO2

Figure 2. Difference in the free energy of the low-temperature monoclinic and the high-
temperature tetragonal phases of zironia. The solid red line includes effects of thermal
expansion. The results shown as dashed line use the computed lattice parameters at T=0 K.

Computed results accurately described than the absolute value of a

The present first-principles calculations
correctly predict the monoclinic phase of ZrO2
to be more stable at low temperatures with the
tetragonal phase becoming more favorable at
high temperatures. The computed transition
temperature is 1700 K compared with an
experimental value of 1478 K. This deviation of
15% is a respectable result given the subtle
nature of temperature-induced phase transitions.
Significance
The ability to predict temperature-dependent
phase transitions with a first-principles method
opens the door for systematic studies of the
effect of vacancies, dopants, and external strains
on the transition temperature providing useful
materials property data as well as insight into
the role and mechanism of vacancies, doping,
and mechanical load. Relative trends such as
stress-induced changes are likely to be more
transition temperature.
MedeA modules used for this application
The present calculations were performed with
the MedeA platform using the following
integrated modules of the MedeA software
environment
Standard MedeA framework including
crystal structure builders and geometric
analysis tools as well as JobServer and
TaskServers
InfoMaticA with structural databases
(ICSD, Pearson, Pauling) in this case each
of these databases contains the various
phases of ZrO2
VASP 4.6 and its graphical user interface as
integrated in MedeA
Phonon as integrated in MedeA

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Materials Design Application Note Phase Transitions in ZrO2

Comments calculation of the vibrational entropy is critical.

This task is accomplished with the MedeA-
The phase transition of ZrO2 from the
Phonon module, which computes the full
monoclinic to the tetragonal structure is driven
phonon dispersions of crystalline structures.
by vibrational entropy. For a given temperature
Integration over all phonon branches gives a
the vibrational entropy of the tetragonal phase is
phonon density of states, which leads directly to
larger than that of the monoclinic phase. The
the temperature-dependent terms of the
electronic energy of the monoclinic phase is
enthalpy, the zero-point energy, and the
lower than that of the tetragonal phase even if
vibrational entropy as a function of temperature.
the lattice expands. Therefore, an accurate
These results are shown in Fig. 3.

Figure 2. Phonon dispersions and phonon densities of states for monoclinic and tetragonal
ZrO2 computed from first-principles using MedeA with VASP and Phonon. Note that the
monoclinic phase shows higher frequencies than the tetragonal phase.

dependent functions of the enthalpy and entropy

The coefficient of thermal expansion for the two
are then used to include the effects of thermal
phases of zirconia are obtain from a series of
expansion.
electronic structure and phonon calculations for
different lattice parameters. Minimization of the
The high-temperature cubic phase is
free energy for each temperature gives an
dynamically stabilized by cooperative
equilibrium lattice parameter for that
displacements of chains of oxygen atoms
temperature. The computed temperature-
oscillating in a double-well potential. The

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Materials Design Application Note Phase Transitions in ZrO2

prediction of this second phase transition is References

more complicated and requires a theoretical 1. Binary Alloy Phase Diagrams, Second Edition,
approach beyond the quasi-harmonic Ed. T. B. Massalski, ASM International, Materials
approximation used in the present work. Park, Ohio (1990) 3, 2940-2941 as implemented
in the Pauling File Binaries Edition, Version 1.0,
The approach outlined in this application note Release 2002/1, P. Villars (editor-in-chief)
has recently been used by the group of Prof. Isao
2. A. Kuwabara, T. Tohei, T. Yamamoto, and I.
Tanaka at Kyoto University as described in Ref. Tanaka, Ab initio lattice dynamics and phase
[2]. transformations of ZrO2, Phys. Rev. B 71,
064301 (2005)

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